Dithiocarbamates coupling with

Ammonium pyrrolidine dithiocarbamate (APDC) chelate coprecipitation coupled with flameless atomic absorption provides a simple and precise method for the determination of nanomol kg 1 levels of copper, nickel, and cadmium in seawater. With practice, the method is not overly time-consuming. It is reasonable to expect to complete sample concentration in less than 20 min, digestion in about 4 h, and sample preparation in another hour. Atomic absorption time should average about 5 min per element. Excellent results have been obtained on the distribution of nickel and cadmium in the ocean by this technique. 

Bruland et al. [122] have shown that seawater samples collected by a variety of clean sampling techniques yielded consistent results for copper, cadmium, zinc, and nickel, which implies that representative uncontaminated samples were obtained. A dithiocarbamate extraction method coupled with atomic absorption spectrometry and flameless graphite furnace electrothermal atomisation is described which is essentially 100% quantitative for each of the four metals studied, has lower blanks and detection Emits, and yields better precision than previously published techniques. A more precise and accurate determination of these metals in seawater at their natural ng/1 concentration levels is therefore possible. Samples analysed by this procedure and by concentration on Chelex 100 showed similar results for cadmium and zinc. Both copper and nickel appeared to be inefficiently removed from seawater by Chelex 100. Comparison of the organic extraction results with other pertinent investigations showed excellent agreement. 

A rapid technique has been developed for quantitatively concentrating several trace metals from aqueous solution. The metals are co-precipitated as dithiocarbamate chelates by adding an excess of another dissolved metal. This technique has been coupled with atomic absorption analysis for the precise determination of nmol/kg quantities of copper in seawater. Radiotracer experiments show that nickel, iron, and cadmium are also co-precipUated by this technique under proper experimental conditions. 

Recently, Ma et al. developed a three-component reaction for the synthesis of 2-A -substituted benzothiazoles 107 via the copper-catalyzed coupling of 2-iodoanilines, carbon disulfide, and secondary amines (Scheme 3.56) [149]. In these reactions, the condensation of CS with an amine in the presence of a base generates dithiocarbamate salts XXXV, which undergo coupling with 2-iodoanilines to give XXXVI and subsequent intramolecular condensation and elimination to afford the substituted benzothiazoles 107. 

Tian-Hong Zhang et al. [652] have reported a new ion exchange chelating fibre with aminophosphonic and dithiocarbamate groups, based on polyacrylonitrile for the preconcentration of rare earth elements in seawater prior to their determination by inductively coupled plasma mass spectrometry. Rare... 

Tseng et al. [69] determined 60cobalt in seawater by successive extractions with tris(pyrrolidine dithiocarbamate) bismuth (III) and ammonium pyrrolidine dithiocarbamate and back-extraction with bismuth (III). Filtered seawater adjusted to pH 1.0-1.5 was extracted with chloroform and 0.01 M tris(pyrrolidine dithiocarbamate) bismuth (III) to remove certain metallic contaminants. The aqueous residue was adjusted to pH 4.5 and re-extracted with chloroform and 2% ammonium pyrrolidine thiocarbamate, to remove cobalt. Back-extraction with bismuth (III) solution removed further trace elements. The organic phase was dried under infrared and counted in a ger-manium/lithium detector coupled to a 4096 channel pulse height analyser. Indicated recovery was 96%, and the analysis time excluding counting was 50-min per sample. 

The direct reaction of [TCO4] in ethanolic solution with dppe and oxalic acid produces the red Tc" complex [Tc(ox)(dppe)2] (552). Attempts to prepare similar complexes with succinic acid, phthalic acid, or salicylic acid failed, or the complexes were stable in solution only. " Similarly, cationic complexes of Tc" are produced by reaction of the versatile precursor [TcO(OH)(dppe)2] (204) with various dithiocarbamates, which produces several complexes of general formula [Tc(dtc)(dppe)2] (553). For this reaction the reductant formamidine sulphinic acid (510) was required in an alkaline solution. The X-ray crystal structure of [Tc(S2CNMe2)(dppe)2] (554) shows a distorted octahedral geometry. Cyclic voltammetry reveals a reversible reduction wave Tc"/Tc couple at —0.53 V, and a reversible oxidation at +0.3 V for the Tc" /Tc" couple. The same compound (554) was also prepared from the thiourea precursor [TcO(tmtu)4] + (91).The reaction of this precursor in dmf in the presence of dppe produced a mixture of brown [TcO(dtc)(tmtu)2] and the Tc" complex (553). The first compound is probably an intermediate... 

When Ph15NH2 and Na15N02 are used for preparation and nitrosation of the arylhydrazinium dithiocarbamates 38, each of the nitrogen positions of product 39 may be labeled with 1SN to allow measurement of 1SN-1SN coupling constants (Section 6.08.3.2) <1996JST167>. 

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